The preparation of polyurethanes and polyurethane/urea elastomers by reacting an aliphatic diisocyanate with a polyol and then chain extending with a short chain diol or diamine, e.g., an aromatic diamine to form the elastomer is well known. Two processes are used, namely, the prepolymer process and the one shot process which includes reaction injection molding (RIM). A reactant system widely used in the prepolymer process utilizes a cyclohexanediisocyanate as the isocyanate component of the prepolymer and polytetramethylene glycol and polyethylene adipate glycol as the polyol component. (Such a system is sold under the trademark Elate by AKZO N.V. Then, the prepolymer is contacted with an aliphatic diol chain extender and the formulation molded.
The prepolymers using cyclohexanediisocyanates especially trans-1,4-cyclohexanediisocyanate as the isocyanate component have suffered because cyclohexanediisocyanates are volatile and toxic thus requiring special handling procedures. The prepolymers containing unreacted trans-1,4-cyclohexanediisocyanate are difficult to process because of their high melting points and high viscosities at ambient temperatures.
The prior art has produced a variety of prepolymer systems from aliphatic diisocyanates (e.g., cyclohexanediisocyanates and long chain polyols) and such prior art then includes the following patents and articles:
U.S. Pat. No. 3,651,118 discloses a process for the preparation of 1,3-cyclohexylene diisocyanates wherein the corresponding cyclohexanediamines are contacted with hydrogen chloride to form the dihydrochloride salt with subsequent reaction with phosgene to produce the diisocyanate. At column 3, the patentees indicate that the diisocyanates are useful for a variety of applications, and particularly in the preparation of polyurethanes, polyureas, and polyurethane/ureas.
U.S. Pat. No. 4,603,189 discloses various araliphatic polyisocyanates which are triisocyanates. The isocyanates are suited for producing polyurethane lacquers and are alleged to have increased resistance to yellowing in comparison to aromatic polyisocyanates and increased reactivity and hence shorter drying times than lacquers based on aliphatic polyisocyanates. These triisocyanates are methylene-bridged phenyl-cyclohexyl triisocyanates where the phenyl ring has two isocyanate groups. An example is diisocyanato-methylbenzyl-cyclohexylisocyanate.
U.S. Pat. No. 4,518,740 discloses moisture hardening varnishes having an isocyanate resin base of adducts of a mixture of diisocyanates, e.g., 2-methyl-1,5-diisocyanatopentane and 2-ethyl-1,4-diisocyanatobutane. In the background portion of the patent the patentees point out that cyclic polyisocyanates such as isophorone diisocyanate and methylene-bis-(4-cyclohexylisocyanate) are widely used for preparing polyurethanes, but the isocyanurate and the propanetriol prepolymers form hard brittle films following moisture hardening. When cyclic polyisocyanates are reacted with higher molecular weight polyols, hard or soft films can be produced, but the resulting resins are inactive and must be activated with tin catalysts, etc.
U.S. Pat. No. 4,487,913 discloses a polyester polyurethane prepared by reacting trans-1,4-cyclohexanediisocyanate with a mixed polyester polyol. The resulting polyurethane can also contain small amounts of epoxies or a carbodiimide. In the background portion of the invention, the patentee indicates that methylene-bis-(4-isocyanatocyclohexane) sold under the trademark DESMODUR W.TM. by Mobay Chemical Company was suited for producing polyurethanes but had poor fuel resistance even though hydrolytic resistance was acceptable.
U.S. Pat. No. 4,487,910 discloses a process for producing polyurethane prepolymers based on monocyclic and dicyclic aromatic and aliphatic diisocyanates wherein the prepolymer has reduced residual monomer content. Various polyisocyanates such as toluenediisocyanate or methylene-bis(phenylisocyanate) and 4,4'-dicyclohexyl-methane diisocyanates are used in preparing the prepolymer.
U.S. Pat. No. 4,256,869 discloses the preparation of polyurethanes from trans-cyclohexane-1,4-diisocyanate wherein the trans-isomer content is at least 90% of the isocyanate content. It was reported in the background of the invention that processes for producing polyurethanes through the use of cyclohexanediisocyanates via a reaction with polyether and polyester polyols were known, but that these resulting polyurethane systems did not exhibit advantageous properties. However, advantages were achieved through the use of the trans-isomer of cyclohexane-1,4-diisocyanate. For example, polyurethanes produced using the trans-isomer of cyclohexane-1,4-diisocyanate had high softening temperatures with low freezing and glass transition temperatures and that they exhibited a remarkable degree of hardness and abrasion resistance over a wide temperature range.
A series of articles, e.g., Syed, et al., "A New Generation of Cast Elastomers," presented at the Polyurethane Manufacturer's Association Fall Meeting-Boston (Oct. 29, 1985), Dieter, et al., "Aliphatic Polyurethane Elastomers with High Performance Properties", Polymer Engineering and Science, mid-May-1987, Volume 27, Number 9 (page 673) and Wong, et al. Reactivity Studies and Cast Elastomers Based on trans-Cyclohexane-1,4-Diisocyanate and 1,4-Phenylene Diisocyanate, pages 75-92 disclose the preparation of polyurethane elastomers based upon the trans-isomer of cyclohexane-1,4-diisocyanate and indicate that the diol polyurethanes result in tough elastomers with excellent high temperature properties in a high moisture environment and under extreme dynamic stress.